Method for production of photographic material

ABSTRACT

A method for the production of a photographic material, which comprises, in combination, the steps of A. ROUGHENING A BIAXIALLY STRETCHED POLYSTYRENE FILM SUPPORT, B. IRRADIATING SAID SUPPORT WITH ULTRAVIOLET RAY, C. APPLYING TO THE SURFACE OF SAID FILM AN UNDERCOAT LAYER COMPRISING AT LEAST ONE SOLVENT CAPABLE OF DISSOLVING OR SWELLING POLYSTYRENE AND A RESIN HAVING AN AFFINITY TO GELATIN, AND THEREAFTER D. PROVIDING ON THE UNDERCOAT LAYER A PHOTOGRAPHIC LAYER COMPRISING AN EMULSION OR SUSPENSION CONTAINING GELATIN AS A BINDER.

11% States aent 11 1 Tatsuta et a1.

[ METHOD FOR PRODUCTION OF PHOTOGRAPHIC MATERIAL 73 Assignee: Fuji Photo Film c0., Ltd.,

Kanagawa, Japan 22 Filed: Oct. 7, 1971 21 Appl. No.: 187,507

[30] Foreign Application Priority Data Oct. 7, 1970 Japan 4588134 [52] U.S. Cl. 117/34, 117/47 A, 1l7/93.1 CD, ll7/93.31,117/138.8 UA, 96/87 R [51] Int. Cl B44d 1/12, G03c 1/80 [58] Fieldof Search 117/47 A, 34, 93.1 CD,

117/93.31, 138.8 UA; 96/87 R [56] References Cited UNITED STATES PATENTS 3,033,703 5/1962 Schneble et a1. 117/47 A 3,075,855 l/l963 Agens 117/47 A 3,132,983 10/1960 Osborne et al. 117/47 A 3,262,808 7/1966 Crooks et al....... ll7/93.l CD 3,415,683 12/1968 Coffman et al. 117/93.1 GD 3,462,286 8/1969 DeGeest et al. 117/34 3,475,193 10/1969 Takenaka 117/47 A [4 1 Feb. 18, 1975 Primary Examiner-Wil1iam R. Trenor Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A method for the production of a photographic material, which comprises, in combination-the steps of a. roughening a biaxially stretched polystyrene film support, 1

b. irradiating said support with ultraviolet ray,

0. applying to the surface of said film an undercoat layer comprising at least one solvent capable of dissolving or swelling polystyrene and a resin having an affinity to gelatin, and thereafter d. providing on the undercoat layer a photographic layer comprising an emulsion or suspension containing gelatin as a binder.

5 Claims, No Drawings METHOD FOR PRODUCTION Oli PHOTOGRAPHIC MATERIAL BACKGROUND OF THE INVENTION 1. Field of the. Invention The present invention relates to a process for the production of a photographic material.

2. Description of the Prior Art Baryta paper has been used heretofore as a support for various photographic materials such as photographic paper and diffusion-transfer photographic paper. Baryta paper is produced by coating paper made from pulp with a mixture obtained by kneading finely divided barium sulfate, a small amount of binder, such as gelatin and water. I

Such a support, however, suffers from various defects including expansion andcontraction due to moisture variation, shrinkage brought about after development procedure, a requirement of long periods of time for drying after development, and poor resistance to water.

We, the inventors, have now achieved, after making an extensive study, an invention whereby the abovementioned problems accompanied with conventional baryta paper can be overcome.

SUMMARY OF THE INVENTION According to the present invention, there is provided a method for the production of a photographic material, which comprises (a) irradiating ultraviolet ray to a biaxially stretched polystyrene film having a roughened surface, (b) applying to the resulting polystyrene film an undercoat liquid composed of a solution or dis persion in an organic solvent of a resin capable of bonding therewith a photographic emulsion, and (c) thereafter coating further with an emulsion or suspension containing gelatin.

The phrase an emulsion or suspension containing gelatin as a binder is intended to include an aqueous emulsion or suspension of gelatinwith or without added silver halides, such as silver chloride, silver bro mide, silver chlorobromide and silver iodobromide, a light-sensitive diazo compound, a developing nucleus for an image-accepting elementused in a silver halide diffusion transfer process or other necessary components.

The present invention will be described in detail as follows.

DETAILED DESCRIPTION OF THE INVENTION The biaxially stretched polystyrene film having a roughened surface can be obtained by stretching polystyrene film, which has previously been formed from polystyrene resin, according to a conventional process used for biaxially stretching plastics and then subjecting the stretched film to various roughening treatments.

The biaxial stretching maybe carried out by either simultaneous stretching in both dimensions or sequential stretching first in one direction, then in the other direction.

The roughening of the film surface may be effected by contacting the stretched film with an organic solvent capable of dissolving or swelling the polystyrene resin to thereby swell the film, then contacting the swelled film with water or another organic solvent incapable of dissolving the polystyrene resin, but having compatibility with the organic solvent used in the foregoing swelling treatment to thereby impart a roughened film surface.

Typical examples of the former type solvents, i.e., those which dissolve or swell the polystyrene resin, include tetrahydrofuran, methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl chloride, ethylene chloride, cyclohexane, benzene, dimethyl formamide and mixtures thereof. The latter type solvents, i.e., those incapable of dissolving polystyrene, but well compatible with the former solvents, typically include methanol and ethanol. The contact between the film and the solvent may be effected by dipping the film in the organic solvent, applying the organic solvent to the film with roller coaters or brushers, or by spraying the organic solvent by means of sprayers. I

There may also be used other roughening treatments other than by using organic solvents, for example, by mechanical abrasion, by the addition of a foaming agent capable of generating gas upon heating to thereby cause whitening all over the film, or by the selective dissolution of a third substance which has been admixed to the film structure before forming to thereby generate a coarse surface. Any one of the abovementioned roughening treatments may be employed without negating from the substantial value and goals of the present invention.

The polystyrene resin may contain white pigment such as, for example, titanium dioxide, barium sulfate, calcium sulfate, barium carbonate, lithopone, alumina white, calcium carbonate, silica white and the like, and,

if necessary, a colored pigment.

Whitening or opalizing of the film in accordance with the foregoing processes imparts a satisfactory picture scene to the photographic material produced from the thus prepared resin.

Polystyrene resin generally has excellent properties in water resistance, dimensional stability, stiffness and the like. Accordingly, the film treated as above exhibits superior whiteness and opacity, and hence is extremely desirable for use as a support for a photographic mate rial. On the other hand, polystyrene resin gives rise to another problem that when the polystyrene support which is inherently hydrophobic and chemically inactive is coated with a hydrophilic emulsion containing gelatin, the adhesion between the coated film and the polystyrene support is very poor.

In case of employing transparent polystyrene as a photographic support, a process has been proposed where a liquid, which dissolves or swells polystyrene,

prepared by dissolving or dispersing a resin being adherent to aphotographic emulsion, such as gelatin (this liquid is referred to hereinafter as the undercoat liquid) is coated onto the surface of a polystyrene support so 'as to provide one or more undercoat layers by which the adhesion between the polystyrene support and the photographic emulsion layer is secured.

Such undercoating processes for transparent polystyrene film have been disclosed in a number of patents, including US. Pat. Nos. 2,872,318, 2,875,056, 3,010,838; British Pat. No. 819,592, and so on.

In order to attain satisfactory adhesion between the transparent polystyrene support and the photographic emulsion layer in the above undercoating process, however, it is necessary to employ a great amount of strong solvent for polystyrene, for example, toluene, ethylene dichloride, ethyl acetate, acetone etc., which in turn results in serious deterioration in the transparency and mechanical strength of the support owing to the generation of a great number of minute crackings on the sur- -C OOH -NH -C ON face of polystyrene support (so-called solvent cracking). For this reason, the type and the composition of the solvent to be practically adopted as the undercoat solvent is limited within an extremely narrow range.

According to the present invention, very excellent adhesion between the polystyrene support and an emulsion or suspension containing gelatin can be attained by a process comprising, in combination, the

steps of l. roughening the surface ofa biaxially stretched polystyrene support,

2. irradiating the support with ultraviolet ray to thereby activate the surface, r

3. coating thereon, with an undercoat liquid containing an organic solvent and a resin having affinity to gelatin, and (4) finally coating with an emulsion or suspension containing gelatin. It is impossible to obtain sufficient adhesion between the support and the photographic emulsion coating layer even if any one of the procedures of steps (1), (2) and (3) as mentioned above is omitted.

According to the process of this invention, it is now possible to use a wide variety of undercoat solvents compared to prior undercoat processes wherein neither roughening nor ultraviolet ray irradiation is conducted, and by this result it is also possible to use an undercoat liquid containing a solvent having less solubility to polystyrene or containing only a small amount of a.soluble solvent, which in turn results in avoiding the generation of new cracking on the surface of the support as well as in preventing the lowering of mechanical strength, while ensuring good adhesion.

In the process of this invention, since the effect of roughening the surface .of the polystyrene film support is exerted in cooperation with the effect of ultraviolet ray irradiation, good adhesion can be attained only when the foregoing three steps of l (2) and (3) are employed together.

In orderv to impart such adhesiveness to a hydrophobic polymer, the surface of the polymer should generally be rendered hydrophilic by resorting to some surfacial treatments, which are usually observed by the reduction in the contact angle of the polymer with water. However, it is quite unexpected that the improvement in adhesiveness is attained according to the process of this invention, even though'there is no change in the angle of the contact with water, which corresponds to the degree of the wet state of the polystyrene support, which is observed at the time before or after the irradiation of the support with ultra-violet rays.

Some improvement in the adhesion was also noticed as to a sample obtained by irradiating ultraviolet ray to unroughened transparent polystyrene followed by coating with the afore-mentioned undercoat liquid, in comparison with the case where no irradiation with ultravi- (R andR -SO M (M: hydrogen or alkali metal),

each hydrogen or alkyl group 2 containing up to 4 carbon atoms) and having affinity to gelatin and also capable of being dispersed or dissolved in an organic solvent, and gelatin or casein.

Specific examples of such resins are cellulose acetate maleate, vinylic copolymers containing maleic anhydride, copolymers of acrylamide with methacrylic acid, a mixture of polyvinyl pyrollidone with polyacrylic acid and the like.

Preferred solvents to be used as a composition in the undercoat liquid include water, alcohols, ketones, phenols, carboxylic acid esters, chlorinated paraffins, aromatic hydrocarbons, etc. Typical of these are methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, phenol, o-chlorophenol, p-chlorophenol, methyl acetate, butyl acetate, methylene dichloride, ethylene dichloride,chloroform, benzene, toluene, xylene, etc. Mixtures of two or more of these solvents may be used as well.

The photographic material using a roughened and undercoated polystyrene support demonstrated sufficiently high adhesion between the film support and the coated layer in' both the dry state and wet state during developing treatment, and the strength of the adhesion did not lower at all after a long period of time. It can be said that the photographic material'obtained in accordance with the present invention has an excellent photographic performance because fogging and drop of sensitivity, which constitute fatal drawbacks can be eliminated owing to the use ofa white and opaque photographic support with good adhesion, which can be attained by the method of this invention without adding any foreign substances thereto.

The present invention will be more explicity set forth in further detail by referring to the following examples, which are merely illustrative and not [imitative thereof. The test of adhesion strength between the polystyrene film and the coating layer set forth in the examples was carried out as follows:

'1. Adhesion Test for Dry State A cellulose triacetate film of 0.14 mm in thickness was bonded using an epoxy type resin adhesive onto the coated surface of a sample prepared by coating a gelatin-containing emulsion as a binder on a polystyrene film support. The bonded film was allowed to stand overnight at a temperature of 23C and relative humidity of and then cut into a strip of 1 cm in width obtained.

and 15 cm in length. The cellulose triacetate film was then peeled off at a pull speed of 7.38 cm per minute while measuring the force of peeling resistance by means of a strain gauge.

In the following examples, the term good adhesion" refers to a case where the sample has a peeling resistance of greater than 8 g/mm which is a sufficient adhesion strength for the use as a photographic material.

2. Adhesion Test for Wet State EXAMPLE 1 A biaxially stretched polystyrene support of 0.1 mm in thickness was dipped for 3 seconds in a solvent consisting of 7 parts ethyl acetate and 1 part ethanol, and then dipped for 30 minutes in methanol until the fil became white and opaque.

The resulting film having a roughened surface was irradiated with ultraviolet ray using three I kw quartz mercury lamps placed in parallel at intervals of 50 cm along the advancing direction of the film support and at a position 13 cm above the support, which was conveyed at a running speed of 3 'rn/minute. The film support was then coated with an undercoat liquid having the following composition, and dried at room tempera ture.

Gelatin |.4 g Water 3.6 cc, Methanol 164 cc Methylene Chloride 30 cc Salicylic acid 0.5 g Formalin aqueous solution) 0.5 cc

The film thus undercoated was further. coated with a silver halide photographic emulsion having the following composition. The amount is given for each square meter of the film.

Silver chlorobromide 3.5 g Gelatin (binder) 13.0 g Formalin (hardener) 0.l g Saponin (wetting agent for coating) 0.03 g Water to make the emulsion into I cc For the purposes of comparison, the same silver halide photographic emulsion having the above composi- TABLE 1 Peeling off Resistance (g/mm) This invention A B C Dry State 200 4 5 0 0.5 .6 Wet State 0 2 As can be seen from Table l, satisfactory good adhesion was attained in both the dry and wet states according to the method of this invention. No lowering of the adhesion strength was observed after a period of 6 months.

EXAMPLE 2 A biaxially stretched polystyrene film of 0.1 mm in thickness was dipped in toluene for 2 seconds, then dipped in methyl isobutyl ketone for 5 seconds, and thereafter'dipped again in methanol for 30 seconds to give a white and opaque (roughened) support having a fine porous layer on its surface. Thus, the roughened polystyrene .film was irradiated with ultraviolet ray under the same conditions as set forth in Example I, then coated with an undercoat liquid having the following compositions, and thereafter dried at room temper ature.

Gelatin 1.4 g

Water 3.6 cc Methanol 1 l4 cc Methylene chloride 30 cc Methyl acetate 50 cc Salicylic acid I 0.5 g

Formalin (20% aqucous solution) 0.5 cc

EXAMPLE 3 A biaxially stretched polystyrene film of 0.2 mm in thickness was dipped for 3 seconds in a mixed solvent consisting of one part acetone and one part methyl ethyl ketone, then dipped for 30 seconds in methanol to give a white and opaque (roughened) film having a fine porous layer on its surface. Using the thus prepared roughened film as the support, ultraviolet ray was irradiated thereto under the same conditions as set forth in Example 1. Then an undercoat liquid having the followingcomposition was applied to the irradiated film:

Gelatin 2.5 g Water 30 cc Methanol cc Toluene 12.5 cc Salicylic acid 0.6 g Formalin (20% aqueous solution) 0.3 cc

The resulting film was further coated with a coating liquid for forming an image-receiving layer of an image-receiving material to be used in the silver salt diffusion transfer photographic process, and having a composition as follows:

Gelatin (binder) 3 g Colloidal silver sulfide (developing nuclei) 0.001 g Phenylmercaptotetrazole (color conditioner) 0.01 g Saponon (wetting agent) 0.02 g

A peeling off test as to this image-receiving material exhibited satisfactory adhesion in both the dry and wet states, which was sufficient'for use as a silver salt diffusion transfer photographic process. On the other hand, only poor adhesion was obtained when the coating liquid was directly applied to the polystyrene support, which had been subjected to a surface-roughening treatment alone.

EXAMPLE 4 A polystyrene sheet containing 2 2 ,5% by weight of powdery titanium dioxide' wasbiaxially stretched in the lateral and longitudinal directions at an elongation ratio of 1.5 times to give a white polystyrene film support of a thickness of 0.1 mm. This polystyrene film support was dipped first in methyl ethyl ketone for 3 seconds, and ,then in methanol for 30 seconds to provide a roughened polystyrene support containing titanium dioxide pigment. This film was subjected to irradiation with ultraviolet ray according to the manner set forth in Example 1, then coated with the undercoat liquid having the same composition as used'in Example 2, and then driedat room temperature.

The resulting film was coated with a silver halide color photographic composition as follows (given in the amount per square meter of the film):

Silver chlorobromide 3.0 g Gelatin 3.5 g Behzoylaceto-Z-chloro-S-dodecyl-oxycarbonyl anilide (yellow coupler) 14.0 g Triethylene phosphamide (3% acetone solution) 3.0 ml Polyvinyl pyrrolidone 0.7 g

The result of the peeling off test as to the above film coated with the color emulsion showed sufficient adhesion strength in both the dry and wet states to be required for a color photographic material.

On the other hand, there was observed very poor adhesion between the support and the above color photographic emulsion layer of the samples, one of which was prepared by irradiating the same film support with ultraviolet ray without a previous roughening treatment followed by coating the above undercoat liquid. The other was prepared by coating the above undercoat liquid to the roughened film without ultraviolet irradiation.

EXAMPLE 5 A polystyrene film having a roughened surface and irradiated with ultraviolet ray in a manner similar to Example 1 was coated with an undercoat liquid having the following composition and dried at 80C for 2 minutes:

A copolymer consisting of Maleic anhydride 1 part, and

Vinyl acetate 1 part 25 g Methanol 500 cc Acetone 250 cc n-Butanol 50 cc Chromium acetate 2.5 g

The film provided with the above undercoat layer was further coated with a silver halide photographic emulsion set forth in Example I. The peeling off test of the resulting emulsion-coated sample exhibited that the film had sufficient adhesion strength between the sup-- port and the emulsion layer in both dry and wet states EXAMPLE 6 An undercoat liquid with the following composition was applied to a polystyrene support which had been roughened and irradiated with ultraviolet ray in the manner similar to Example 2, and then dried at C for 5 minutes.

A copolymer consisting of Acrylamide 2 parts, and

Methacrylic acid 1 part 20 g Methanol 450 cc lsopropanol 20 cc Phenol 20 g Chromium acetate 1.5 g

The undercoat layer so formed was further coated with a silver halide photographic emulsion as described in Example 1. The resulting emulsion-coated film was then subjected to a peeling off test and proved to have excellent adhesion strength between the support and the emulsion layer in both the dry and wet states, which was sufficient foruse as a photographic material.

On the other hand, the adhesion strength was very poor in cases where the film was obtained after irradiation with ultravioletray and coating with the above undercoat liquid, but subjected to no-surface roughening treatment, and where the film was obtained after the surface roughening treatment, followed by application of the above undercoat liquid, but without ultraviolet irradiation.

Although the present invention has been adequately described in the foregoing-specification'and examples included therein, it is readily apparent that various changes and modifications can be made without departing from the spirit and scope thereof.

What is claimed is: l. A method for the production of a photographic material, which comprises, in combination, the steps of a. roughening a biaxially stretched polystyrene film support, b. irradiating said support with ultraviolet ray, c. applying to the surface of said film an undercoat layer comprising at least one solvent capable of disylformamide and mixtures thereof.

3. The method of claim 1, wherein said solvent incapable of dissolving polystyrene is a lower alkyl alcohol.

4. The method of claim 1, wherein said polystyrene further contains a white pigment.

5. The method of claim 4, wherein said white pigment is a member selected from the group consisting of TiO BaSO CaSO BaCO lithopone, alumina white,

CaCO and silica white. 

1. A METHOD FOR THE PRODUCTION OF A PHOTOGRAPHIC MATERIAL, WHICH COMPRISES, IN COMBINATION, THE STEPS OF A. ROUGHENING A BIAXIALLY STRETVHED POLYSTYRENE FILM SUPPORT, B. IRRADIATING SAID SUPPORT WITH ULTRAVIOLET RAY, C. APPLYING TO THE SURFACE OF SAID FILM AN UNDERCOAT LAYER COMPRISING AT LEAST ONE SOLVENT CAPABLE OF DISSOLVING OR SWELLING POLYSTYRENE AND A RESIN HAVING AN AFFINITY TO GELATIN, AND THEREAFTER D. PROVIDING ON THE UNDERCOAT LAYER A PHOTOGRAPHIC LAYER COMPRISING AN EMULSION OR SUSPENSION CONTAINING GELATIN AS A BINDER.
 2. The method of claim 1, wherein said solvent, which dissolves or swells polystyrene, is a member selected from the group consisting of tetrahydrofuran, lower alkyl acetates, lower alkyl ketones, methyl chloride, ethylene chloride, cyclohexane, benzene, dimethylformamide and mixtures thereof.
 3. The method of claim 1, wherein said solvent incapable of dissolving polystyrene is a lower alkyl alcohol.
 4. The method of claim 1, wherein said polystyrene further contains a white pigment.
 5. The method of claim 4, wherein said white pigment is a member selected from the group consisting of TiO2, BaSO4, CaSO4, BaCO3, lithopone, alumina white, CaCO3, and silica white. 